Detergent composition



Patented Au at, its? warren stares assists DETERGENT coma SITKON Robert A. Duncan and Walter H. McAllister, Wyoming, Ohio, assignors to The Procter 4% Gamble Company, Cincinnati, Ohio, a corporation ct @hio No Drawing. Application August 2%, i934, Serial No. 741,828

12 Elaine's.

This invention relates to wetting and cleansing agents, more particularly to those which depend for cleansing action on soluble saltsoi the high molecular alkyl sulfuric acids.

It is the object of our invention to provide a detergent of the above mentioned type which combines the properties of high solubility, resistance to precipitation in hard water, and unusual- V 1y mild action on the skin.

0 Among the salts of the higher alkyl sulfuric acids proposed for use as wetting and cleansing agents are the ammonium salts, which have the advantage of relatively high solubility in water but are somewhat irritating especially when in contact with the skin in high concentration for long periods of time.

Substituted ammonium salts have also been proposed for use, of which the tri-ethanol ammonium salts are likewise valuable on account of high solubility. The tri-ethanol ammonium salts are somewhat milder in their action on the skin than the corresponding ammonium salts, although this fact does not appear to have been recognized by those interested in these compounds.

We have found that a still further decrease in irritating action on the skin results from increasing the length of carbon chain of the amine, and increasing the number of alcoholic hydroxyls substituted in said carbon chain. Thus we have found that the glyceryl ammonium salts of the alkyl sulfuric acids having from ten to eighteen carbon atoms in the alkyl radical possess the qualities desirable in a good cleansing and wetting agent and because of their high solubility are excellently suitable for shampoos or for use in liquid soap dispensers.

The glyceryl ammonium salts of the sulfuric acid derivatives derived from unsaturated hydrocarbons or saturated and/or unsaturated aliphatic alcohols by the reaction of such compounds with sulfonating or sulfating agents such as concentrated sulfuric acid, sulfurv trioxide, chlorsulfonic acid, etc., possess good sudsing,

emulsifying, and detergent properties and are unusually mild in their action on the skin. Of particular interest and value are the glyceryl ammonium salts of sulfated aliphatic alcohols having from ten to about eighteen carbon atoms.

The glyceryl amine used in the preparation of the compounds herein disclosed may consist of mono-, dior triglyceryl amine or may consist of any mixtures of these. For example, a glyceryl amine prepared by the reaction of ammonia and ammonium hydroxide on glycerol monochlorhydrin, with an average equivalent weight of 135, gives excellent results when used for the neutralization of mono alkyl sulfuric acids. This amine isa complicated mixture of mono-, diand triglyceryl amines, for each of which, one of the isomeric formulas is given below:-

CHc-OH CH2OH cHPoH OHr-OH cm on CH-0H OH-OH OH OH CH-OH OH OH OHNH= CHz-I|\TCH2 CH2N- CH1 Monoglyceryl E H amine molecular weight: Diglyceryl amine CH --0H 91 molecular weight=l I CHPOH Triglyceryl amine molecular weight=239 For the sake of economical operation, we prefer not to separate the individual glyceryl amines, but to use a mixture such as that described above.

The sulfated alcohols we prefer to use in carrying out our invention are derived from normal primary alcohols such as those corresponding to the mixed fatty acids of coconut oil or other oils of the same'class, as defined by Lewkowitsch in Chemical Technology and Analysis of Oils, Fats and Waxes, Sixth Edition, 1922, pages 500 and 617, such as for example palm'kernel oil. Likewise, the fractionated alcohols from these raw materials, containing as the main ingredient, lauryl alcohol, are especially suitable. Other alcoholscontaining from ten to eighteen carbon atoms per molecule may be used depending on the type of product desired. For example, for the preparation of pastes, semi-solid or solid'detergents, the higher molecular weight alcohols or unsaturated hydrocarbons are suitable. For the preparation of liquid detergents, on the other hand, the lower molecular weight alcohols are desirable because of the higher solubility of the sulfated compounds. As a general rule, the solubility of the salts described herein decreases with an'increase in molecular weight of the sulfated alcohol used.

In preparing one type of compound suitable for use as a detergent, Stenol, the commercially available alcohol consisting mainly of the saturated alcohols containing sixteen and eighteen carbon atoms respectively, is used. The alcohol is sulfated in the usual manner with a sulfating agent such as chorsulfonic acid; thisproduct is then thoroughly mixed with a solution of 'glyceryl amine until the alkyl sulfuric acids are neutralized. The product may then be dried to yield a highly soluble detergent which does not irritate the skin.

In the preparation of an aqueous liquid detergent having excellent sudsing and cleansing properties, stability against hard water, and in addition, being mild in its action upon the skin, the alcohols obtained by the reduction of cocoanut oil by known means are fractionated and that portion consisting mainly of lafiryl alcohol is sulfated with chlorsulfonic acid, then neutralized with an aqueous solution of glyceryl mine. The amount of water and other ingredients used is so adjusted as to yield a product having the desired composition. The concentration preferably should be kept below the saturation point of the sulfated product at the lowest temperature at which it may be used. It has been found that a solution of the glyceryl ammonium salt of the sulfated alcohols from cocoanut oil containing about thirty per cent of the anhydrous salt is sufiiciently fluid for use in liquid soap dispensers, does not cloud or precipitate during storage at 50 F., and is less irritating to the skin than a solution of the corresponding triethanol ammonium salt which in turn is less irritating than a solution of the ammonium salt.

We have found that our detergent is an excellent substitute for so-called dry cleaning soaps and inmany cases is to be preferred. Therefore, we do not limit ourselves to aqueous solutions but may prepare also according to the present invention other solutions of the glyceryl ammonium salts such as alcoholic solutions, or solutions of the salts in other solvents, especially those commonly used in the dry cleaning industry.

In the preparation of aqueous liquid detergents of the character described it has sometimes been found advantageous to stabilize the alkyl sulfate against hydrolysis. We have found that, after neutralization to methyl orange, the addition of a slight excess of glyceryl amine or of about one per cent of some other weakly alkaline substance, which will serve to buffer the solution and thus retard decomposition, is preferable. Alkaline substances such as sodium carbonate, sodium bicarbonate, secondary sodium phosphate, other alkali carbonates and bicarbonates, borates, lactates, etc., added in sufficient quantities to obtain a pH value of about seven or eight, may be used. At this point the aqueous solutions have been found to be quite stable.

A low molecular weight aliphatic alcohol, such as for example ethyl alcohol, may be added, if desired, to reduce the viscosity ofthe aqueous solution.

The high molecular weight alcohols which we find to be suitable for the preparation of the products described are lauryl, myristyl, cetyl, oleyl and stearyl alcohols and in general any of the primary aliphatic alcohols, saturated or unsaturated, such as those which can be obtained from the natural oils, fats and waxes by known methods of reduction. Secondary aliphatic alcohols. such as those which can be obtained from petroleum hydrocarbons by oxidation are also suitable. In the case of the primary alcohols, alkyl radicals containing from ten to eighteen carbon atoms are preferable while in the case of the secondary alcohols, due to the greater solubility of the sulfated products, alkyl radicals containing from ten to twenty-five carbon atoms have been found satisfactory. Unsaturated aliphatic hydrocarbons, especially the unsaturated straight chain hydrocarbons containing from ten to eighteen carbon atoms in a chain, are also suitable for the preparation of our products. These unsaturated hydrocarbons, onsulfation,

yield sulfuric esters similar to those obtained by the sulfation of alcohols containing the same number of carbon atoms. The glyceryl ammonium salts. of the alkyl sulfuric acids obtained from the above alcohols and hydrocarbons have high emulsifying properties, are very stable towards the substances causing hardness of water and are mild in their action upon the skin.

Because of the ample sudsing and detergent power of our detergent, soap is not only an unnecessary ingredient but any appreciable amount of soap is found to exert a harmful action in hard water. Our product prepared as described, shows excellent sudsing and detergent properties, is suitable for use even in very hard water such as sea water, either for shampoo or other toilet use, and when used for shampoo easily removes the soil and excess oily material from the hair, leaving same in a clean, soft, fiufiy condition much'superior to that resulting from treatment with shampoos hitherto in common use. The material is easily and completely rinsed from the hair, and as no lime soap is formed, no stickiness can result from its use in hard water, so that a subsequent wash with lemon juice or similar acid material becomes unnecessary when using our product.

It is to be understood that our invention is intended to cover compounds containing inert materials and other ingredients such as perfume, coloring matter, etc., and also intended to cover any detergent which consists essentially of the glyceryl ammonium salts of the alkyl sulfuric acids which salts are characterized by their high solubility and the mildness of their action upon the skin.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is: 3

1. A detergent composition suitable for use on the human skin comprising essentially glyceryl ammonium salts of alkyl sulfuric acids having ten to eighteen carbon atoms per molecule.

2. A composition suitable for use on the human skin and having emulsifying, sudsing, and detergent properties, comprising as the essential ingredient glyceryl ammonium salts of sulfated alcohols obtainable from oils of the cocoanut 011 class.

3. A cleansing agent suitable for use on the human skin comprising essentially glyceryl ammonium salts of a sulfated alcohol having ten to eighteen carbon atoms in the. alkyl radical and derived from cocoanut oil.

4. A liquid detergent suitable for toilet use substantially soap free, comprising an aqueous solution of glyceryl ammonium salt of a sulfuric acid ester of a compound selected from the group consisting of primary aliphatic alcohols, secondary aliphatic alcohols, and unsaturated aliphatic hydrocarbons, which compounds contain from ten to eighteen carbon atoms in the molecule.

5. A liquid detergent substantially free from soap and suitable for use as a shampoo for human hair characterized by its mild action on the skin, comprising an aqueous solution of glyceryl ammonium salts of sulfated alcohols obtainable from oils of the cocoanut oil class.

6. A liquid detergent substantially free from soap and suitable for toilet use, comprising an aqueous solution of glyceryl ammonium salts ofsulfated alcohols having ten to eighteen carbon atoms in the molecule.

'7. A liquid detergent substantially soap free,

suitable for use as a shampoo for human hair and characterized by its mild action on the skin,

comprising an aqueous solution of glyceryl am monium salt of sulfated oleyl alcohol.

8. A liquid detergent substantially free of soap,

suitable for use as a shampoo for human hair and characterized by its mildness towards the skin comprising an aqueous solution of 'glyceryl ammonium salt of sulfated alcohols obtainable 10 from petroleum, which alcohols contain from ten to twenty-five carbon atoms in the chain.

9. A liquid detergent substantially free from soap having substantially no irritating action on normal human skin under ordinary conditions 15 of use andhaving as its essential ingredient an aqueous solution of a detergent agent consisting essentially of a glyceryl ammonium salt of a mixture of alkyl sulfuric acids derived from coconut oil.

10. A liquid detergent suitable for toilet use and stabilized against hydrolysis, comprising Water. a glyceryl ammonium salt 01' a mixture of alkyl sulfuric acids derived from coconut oil, and a sufficient amount 01' a weakly alkaline salt to impart to the liquid detergent a pH value of about 7.

11. A detergent composition suitable for use on the human skin comprising as the essential ingredient a glyceryl ammonium salt of a sulfuric acid ester of a compound selected from the group consisting of primary aliphatic alcohols, secondary aliphatic alcohols and unsaturated aliphatic hydrocarbons, which compounds contain from ten to eighteen carbon atoms in the molecule.

12. A new composition free of appreciable amounts of soap but suitable for use in cleansing the human skin, containing as the principal cleansing agent the glyceryl ammonium salt of sulfated lauryl alcohol.

R031" A. DUNCAN. WALTER. H. McSTEI-t. 

